Ethyl 2-[(E)-4-(dimethyl-amino)benzyl-idenehydrazino]-5-nitro-benzoate.

The title compound, C(18)H(20)N(4)O(4), exists in the E configuration with respect to the C=N bond of the methyl-idine unit. The dihedral angle between the two benzene rings is 9.01 (6)°. An intra-molecular N-H⋯O hydrogen bond involving the benzoate unit generates an S(6) ring motif. In the crystal, the mol-ecules are linked by weak C-H⋯O inter-actions into infinite chains along the b axis. These chains are further connected into sheets parallel to the ab plane which are stacked approximately along the c axis. A C-H⋯π inter-action is also observed.

Related literature

For related literature on hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For background to the applications of hydrazones, see, for example: Barton et al. (1962 ▶); Bedia et al. (2006 ▶); Buu-Hoi et al. (1953 ▶); Paquette (1995 ▶); Rollas et al. (2002 ▶); Terzioglu & Gürsoy (2003 ▶).

Experimental

Crystal data

C18H20N4O4

M = 356.38

Monoclinic,

a = 10.8216 (4) Å

b = 15.9175 (6) Å

c = 10.4136 (4) Å

β = 107.091 (2)°

V = 1714.56 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.10 mm−1

T = 100.0 (1) K

0.44 × 0.41 × 0.31 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T min = 0.957, T max = 0.970

16368 measured reflections

3929 independent reflections

3275 reflections with I > 2σ(I)

R int = 0.029

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.105

S = 1.04

3929 reflections

242 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.26 e Å−3

Δρmin = −0.27 e Å−3

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808035939/is2354sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808035939/is2354Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C18H20N4O4	F000 = 752
Mr = 356.38	Dx = 1.381 Mg m−3
Monoclinic, P21/c	Melting point: 439 K
Hall symbol: -P 2ybc	Mo Kα radiation λ = 0.71073 Å
a = 10.8216 (4) Å	Cell parameters from 3929 reflections
b = 15.9175 (6) Å	θ = 2.0–27.5º
c = 10.4136 (4) Å	µ = 0.10 mm−1
β = 107.091 (2)º	T = 100.0 (1) K
V = 1714.56 (11) Å3	Block, red
Z = 4	0.44 × 0.41 × 0.31 mm

Bruker SMART APEXII CCD area-detector diffractometer	3929 independent reflections
Radiation source: fine-focus sealed tube	3275 reflections with I > 2σ(I)
Monochromator: graphite	Rint = 0.029
Detector resolution: 8.33 pixels mm-1	θmax = 27.5º
T = 100.0(1) K	θmin = 2.0º
ω scans	h = −14→12
Absorption correction: multi-scan(SADABS; Bruker, 2005)	k = −20→19
Tmin = 0.957, Tmax = 0.970	l = −13→13
16368 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.038	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.105	w = 1/[σ2(Fo2) + (0.0493P)2 + 0.6489P] where P = (Fo2 + 2Fc2)/3
S = 1.04	(Δ/σ)max = 0.001
3929 reflections	Δρmax = 0.26 e Å−3
242 parameters	Δρmin = −0.27 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none

Experimental. The low-temperature data was collected with the Oxford Cyrosystem Cobra low-temperature attachment.

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
O1	0.79559 (10)	0.52119 (6)	−0.07387 (11)	0.0354 (3)
O2	0.69063 (9)	0.41140 (6)	−0.17045 (10)	0.0304 (2)
O3	0.81387 (8)	0.14041 (5)	−0.00146 (9)	0.0220 (2)
O4	0.93830 (9)	0.11554 (6)	0.20957 (9)	0.0263 (2)
N1	1.11000 (9)	0.28501 (7)	0.47925 (10)	0.0205 (2)
N2	1.03176 (10)	0.24883 (7)	0.36376 (10)	0.0200 (2)
N3	1.51942 (11)	0.31448 (7)	1.07252 (11)	0.0251 (3)
N4	0.77246 (10)	0.44519 (7)	−0.07681 (11)	0.0233 (2)
C1	1.27580 (12)	0.33820 (8)	0.74183 (12)	0.0211 (3)
H1A	1.2308	0.3810	0.6868	0.025*
C2	1.36107 (12)	0.35818 (8)	0.86484 (12)	0.0217 (3)
H2A	1.3724	0.4141	0.8915	0.026*
C3	1.43165 (11)	0.29502 (8)	0.95126 (12)	0.0199 (3)
C4	1.40814 (11)	0.21103 (8)	0.90855 (12)	0.0205 (3)
H4A	1.4511	0.1679	0.9641	0.025*
C5	1.32196 (11)	0.19195 (8)	0.78513 (12)	0.0204 (3)
H5A	1.3078	0.1360	0.7594	0.024*
C6	1.25546 (11)	0.25480 (8)	0.69791 (12)	0.0190 (3)
C7	1.16926 (11)	0.23101 (8)	0.56787 (12)	0.0200 (3)
H7A	1.1563	0.1742	0.5477	0.024*
C8	0.97180 (11)	0.29570 (8)	0.25563 (12)	0.0186 (2)
C9	0.89357 (11)	0.25738 (8)	0.13494 (12)	0.0185 (2)
C10	0.82866 (11)	0.30810 (8)	0.02772 (12)	0.0188 (2)
H10A	0.7750	0.2839	−0.0500	0.023*
C11	0.84340 (11)	0.39425 (8)	0.03584 (12)	0.0200 (3)
C12	0.92453 (12)	0.43263 (8)	0.15043 (13)	0.0227 (3)
H12A	0.9362	0.4906	0.1531	0.027*
C13	0.98667 (12)	0.38414 (8)	0.25861 (13)	0.0219 (3)
H13A	1.0396	0.4097	0.3355	0.026*
C14	0.88536 (11)	0.16499 (8)	0.12145 (12)	0.0197 (3)
C15	0.80366 (13)	0.05029 (8)	−0.02550 (13)	0.0235 (3)
H15A	0.8831	0.0233	0.0262	0.028*
H15B	0.7926	0.0394	−0.1199	0.028*
C16	0.69201 (16)	0.01346 (9)	0.01292 (16)	0.0362 (4)
H16A	0.6876	−0.0459	−0.0045	0.054*
H16B	0.6132	0.0396	−0.0389	0.054*
H16C	0.7038	0.0230	0.1068	0.054*
C17	1.57956 (12)	0.24807 (9)	1.16534 (13)	0.0243 (3)
H17A	1.6259	0.2111	1.1230	0.036*
H17B	1.5141	0.2169	1.1902	0.036*
H17C	1.6385	0.2722	1.2442	0.036*
C18	1.53899 (13)	0.40099 (8)	1.11646 (13)	0.0276 (3)
H18A	1.5651	0.4334	1.0511	0.041*
H18B	1.6051	0.4037	1.2012	0.041*
H18C	1.4598	0.4233	1.1262	0.041*
H1N2	1.0273 (15)	0.1942 (11)	0.3542 (16)	0.034 (4)*

	U11	U22	U33	U12	U13	U23
O1	0.0480 (6)	0.0165 (5)	0.0349 (6)	−0.0003 (4)	0.0017 (5)	0.0046 (4)
O2	0.0372 (5)	0.0261 (5)	0.0215 (5)	−0.0018 (4)	−0.0011 (4)	0.0025 (4)
O3	0.0290 (4)	0.0158 (4)	0.0178 (4)	−0.0011 (3)	0.0017 (4)	−0.0012 (3)
O4	0.0334 (5)	0.0205 (5)	0.0201 (5)	−0.0013 (4)	−0.0001 (4)	0.0025 (4)
N1	0.0205 (5)	0.0251 (5)	0.0149 (5)	−0.0033 (4)	0.0039 (4)	−0.0025 (4)
N2	0.0239 (5)	0.0194 (5)	0.0152 (5)	−0.0029 (4)	0.0036 (4)	−0.0024 (4)
N3	0.0307 (6)	0.0223 (6)	0.0174 (5)	−0.0018 (4)	−0.0006 (4)	0.0005 (4)
N4	0.0282 (5)	0.0195 (5)	0.0221 (6)	0.0014 (4)	0.0070 (4)	0.0018 (4)
C1	0.0239 (6)	0.0203 (6)	0.0180 (6)	0.0012 (5)	0.0043 (5)	0.0027 (5)
C2	0.0273 (6)	0.0167 (6)	0.0202 (6)	−0.0015 (5)	0.0057 (5)	−0.0005 (5)
C3	0.0220 (6)	0.0222 (6)	0.0150 (6)	−0.0018 (5)	0.0047 (5)	0.0006 (5)
C4	0.0233 (6)	0.0196 (6)	0.0182 (6)	0.0015 (4)	0.0054 (5)	0.0038 (5)
C5	0.0239 (6)	0.0181 (6)	0.0198 (6)	−0.0018 (5)	0.0075 (5)	−0.0005 (5)
C6	0.0199 (5)	0.0214 (6)	0.0163 (6)	−0.0017 (4)	0.0060 (5)	−0.0002 (5)
C7	0.0221 (5)	0.0198 (6)	0.0190 (6)	−0.0024 (5)	0.0076 (5)	−0.0019 (5)
C8	0.0186 (5)	0.0216 (6)	0.0166 (6)	−0.0004 (4)	0.0065 (5)	−0.0006 (5)
C9	0.0198 (5)	0.0188 (6)	0.0172 (6)	−0.0013 (4)	0.0059 (5)	−0.0006 (5)
C10	0.0215 (5)	0.0196 (6)	0.0154 (6)	−0.0015 (4)	0.0054 (5)	−0.0015 (5)
C11	0.0228 (6)	0.0194 (6)	0.0179 (6)	0.0014 (4)	0.0063 (5)	0.0026 (5)
C12	0.0270 (6)	0.0171 (6)	0.0244 (7)	−0.0019 (5)	0.0081 (5)	−0.0026 (5)
C13	0.0246 (6)	0.0218 (6)	0.0185 (6)	−0.0023 (5)	0.0050 (5)	−0.0045 (5)
C14	0.0204 (5)	0.0206 (6)	0.0172 (6)	−0.0017 (4)	0.0043 (5)	−0.0012 (5)
C15	0.0338 (7)	0.0145 (6)	0.0197 (6)	0.0004 (5)	0.0042 (5)	−0.0025 (5)
C16	0.0544 (9)	0.0263 (7)	0.0337 (8)	−0.0135 (6)	0.0218 (7)	−0.0090 (6)
C17	0.0249 (6)	0.0279 (7)	0.0172 (6)	0.0014 (5)	0.0018 (5)	0.0031 (5)
C18	0.0311 (7)	0.0266 (7)	0.0199 (7)	−0.0030 (5)	−0.0003 (5)	−0.0031 (5)

O1—N4	1.2340 (14)	C7—H7A	0.9300
O2—N4	1.2316 (14)	C8—C13	1.4162 (17)
O3—C14	1.3445 (14)	C8—C9	1.4294 (16)
O3—C15	1.4548 (14)	C9—C10	1.3896 (17)
O4—C14	1.2170 (15)	C9—C14	1.4775 (17)
N1—C7	1.2861 (16)	C10—C11	1.3803 (17)
N1—N2	1.3770 (14)	C10—H10A	0.9300
N2—C8	1.3476 (16)	C11—C12	1.3973 (17)
N2—H1N2	0.874 (17)	C12—C13	1.3682 (18)
N3—C3	1.3739 (15)	C12—H12A	0.9300
N3—C18	1.4469 (17)	C13—H13A	0.9300
N3—C17	1.4511 (16)	C15—C16	1.499 (2)
N4—C11	1.4469 (16)	C15—H15A	0.9700
C1—C2	1.3779 (17)	C15—H15B	0.9700
C1—C6	1.4003 (17)	C16—H16A	0.9600
C1—H1A	0.9300	C16—H16B	0.9600
C2—C3	1.4141 (17)	C16—H16C	0.9600
C2—H2A	0.9300	C17—H17A	0.9600
C3—C4	1.4084 (17)	C17—H17B	0.9600
C4—C5	1.3817 (17)	C17—H17C	0.9600
C4—H4A	0.9300	C18—H18A	0.9600
C5—C6	1.3999 (17)	C18—H18B	0.9600
C5—H5A	0.9300	C18—H18C	0.9600
C6—C7	1.4509 (16)
C14—O3—C15	116.37 (9)	C11—C10—H10A	119.8
C7—N1—N2	113.34 (10)	C9—C10—H10A	119.8
C8—N2—N1	121.31 (10)	C10—C11—C12	121.27 (11)
C8—N2—H1N2	117.3 (11)	C10—C11—N4	118.87 (11)
N1—N2—H1N2	120.9 (11)	C12—C11—N4	119.86 (11)
C3—N3—C18	120.17 (11)	C13—C12—C11	119.34 (12)
C3—N3—C17	120.11 (11)	C13—C12—H12A	120.3
C18—N3—C17	119.16 (10)	C11—C12—H12A	120.3
O2—N4—O1	122.76 (11)	C12—C13—C8	121.17 (11)
O2—N4—C11	118.95 (10)	C12—C13—H13A	119.4
O1—N4—C11	118.29 (11)	C8—C13—H13A	119.4
C2—C1—C6	121.36 (11)	O4—C14—O3	122.77 (11)
C2—C1—H1A	119.3	O4—C14—C9	124.77 (11)
C6—C1—H1A	119.3	O3—C14—C9	112.45 (10)
C1—C2—C3	121.09 (12)	O3—C15—C16	111.47 (11)
C1—C2—H2A	119.5	O3—C15—H15A	109.3
C3—C2—H2A	119.5	C16—C15—H15A	109.3
N3—C3—C4	121.08 (11)	O3—C15—H15B	109.3
N3—C3—C2	121.52 (11)	C16—C15—H15B	109.3
C4—C3—C2	117.40 (11)	H15A—C15—H15B	108.0
C5—C4—C3	120.82 (11)	C15—C16—H16A	109.5
C5—C4—H4A	119.6	C15—C16—H16B	109.5
C3—C4—H4A	119.6	H16A—C16—H16B	109.5
C4—C5—C6	121.61 (11)	C15—C16—H16C	109.5
C4—C5—H5A	119.2	H16A—C16—H16C	109.5
C6—C5—H5A	119.2	H16B—C16—H16C	109.5
C5—C6—C1	117.65 (11)	N3—C17—H17A	109.5
C5—C6—C7	119.07 (11)	N3—C17—H17B	109.5
C1—C6—C7	123.27 (11)	H17A—C17—H17B	109.5
N1—C7—C6	122.92 (11)	N3—C17—H17C	109.5
N1—C7—H7A	118.5	H17A—C17—H17C	109.5
C6—C7—H7A	118.5	H17B—C17—H17C	109.5
N2—C8—C13	120.55 (11)	N3—C18—H18A	109.5
N2—C8—C9	120.92 (11)	N3—C18—H18B	109.5
C13—C8—C9	118.53 (11)	H18A—C18—H18B	109.5
C10—C9—C8	119.18 (11)	N3—C18—H18C	109.5
C10—C9—C14	119.99 (11)	H18A—C18—H18C	109.5
C8—C9—C14	120.79 (11)	H18B—C18—H18C	109.5
C11—C10—C9	120.39 (11)
C7—N1—N2—C8	−173.78 (11)	N2—C8—C9—C14	−5.29 (17)
C6—C1—C2—C3	0.22 (19)	C13—C8—C9—C14	173.76 (11)
C18—N3—C3—C4	−177.96 (12)	C8—C9—C10—C11	2.42 (17)
C17—N3—C3—C4	−6.57 (18)	C14—C9—C10—C11	−175.19 (11)
C18—N3—C3—C2	1.74 (19)	C9—C10—C11—C12	0.79 (18)
C17—N3—C3—C2	173.13 (12)	C9—C10—C11—N4	−178.88 (11)
C1—C2—C3—N3	178.24 (12)	O2—N4—C11—C10	7.77 (17)
C1—C2—C3—C4	−2.05 (18)	O1—N4—C11—C10	−173.19 (12)
N3—C3—C4—C5	−178.50 (11)	O2—N4—C11—C12	−171.90 (11)
C2—C3—C4—C5	1.79 (18)	O1—N4—C11—C12	7.14 (18)
C3—C4—C5—C6	0.30 (19)	C10—C11—C12—C13	−2.54 (19)
C4—C5—C6—C1	−2.13 (18)	N4—C11—C12—C13	177.12 (11)
C4—C5—C6—C7	178.08 (11)	C11—C12—C13—C8	1.02 (19)
C2—C1—C6—C5	1.87 (18)	N2—C8—C13—C12	−178.82 (11)
C2—C1—C6—C7	−178.35 (12)	C9—C8—C13—C12	2.13 (18)
N2—N1—C7—C6	−179.18 (10)	C15—O3—C14—O4	−0.73 (17)
C5—C6—C7—N1	−176.20 (11)	C15—O3—C14—C9	178.13 (10)
C1—C6—C7—N1	4.02 (19)	C10—C9—C14—O4	−179.76 (12)
N1—N2—C8—C13	−0.74 (17)	C8—C9—C14—O4	2.67 (19)
N1—N2—C8—C9	178.29 (10)	C10—C9—C14—O3	1.40 (16)
N2—C8—C9—C10	177.12 (11)	C8—C9—C14—O3	−176.17 (10)
C13—C8—C9—C10	−3.83 (17)	C14—O3—C15—C16	88.66 (13)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O4	0.875 (18)	1.978 (17)	2.6736 (14)	135.6 (14)
C7—H7A···O1i	0.93	2.49	3.3599 (16)	156
C12—H12A···O4ii	0.93	2.59	3.3961 (16)	145
C16—H16C···O2iii	0.96	2.59	3.5116 (19)	162
C17—H17B···Cg1iii	0.96	2.64	3.4629 (14)	144

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O4	0.875 (18)	1.978 (17)	2.6736 (14)	135.6 (14)
C7—H7A⋯O1i	0.93	2.49	3.3599 (16)	156
C12—H12A⋯O4ii	0.93	2.59	3.3961 (16)	145
C16—H16C⋯O2iii	0.96	2.59	3.5116 (19)	162
C17—H17B⋯Cg1iii	0.96	2.64	3.4629 (14)	144

Symmetry codes: (i) ; (ii) ; (iii) . Cg1 is the centroid of the C1–C6 ring.